Replacement of the heteroatom from Si to Ge has a strong influence on the luminescence properties of a series of hybrid, sandwich-type K5[Ln(α-GeW11O39)(C20H22Br2N2O4)]·14H2O (1Ge-Ln, Ln = Sm to Lu) anions. Interestingly, the Gd and Yb derivatives retain their ability to display slow relaxation of magnetisation.